Two new group separation schemes, based on ion exchange chromatography, for the selective and quantitative isolation of rare earth elements (REE) from accompanying elements, were devised. After checking their performance with the aid of radioactive tracers, the schemes were further used together with ICP-MS, NAA and ion exchange chromatography for the determination of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu in two certified reference materials (CRMs). The results were compared with another series of analyses, where the REEs were determined directly, i.e. without pre-separation, by instrumental neutron activation analysis (INAA) and inductively coupled plasma mass spectrometry (ICP-MS). It was demonstrated that while direct INAA and ICP-MS in most instances provide reliable results for the majority of REEs, for some elements, notably Sc, Yb and Tm in the cases of ICP-MS and INAA, respectively, systematic errors occur or may potentially occur.